Extraction of petroleum from solid materials



Oct. 11, 1938. H ROSEN-[HAL 'l 2,13%441.

EXTRACTION OF PETROLEUM FROM SOLID MATERIALS Filed Aug. 4, 1934 l 4ToPPlG UNIT Patented Oct. 11,

My invention relates to and .methods of extraction utilizing as solventlo 'particularly those QS at atmospheric pressur is particularly relatedwhich EXTRACTION OF kPAT1.=;1\1'1 OFFICE PETROLEUM FROM SOLID MATERIALSHenry Rosenthal, New York, N. Y.

are normally es and tem peratures. the extraction gaseous It ofpetroleum oil from oil shale in a continuous manner and in a processfrom the extract as a part of 1,0 `rlng, and where the solvent is recovportion of the petroleum reningy p My invention provides means ,o

petroleum oil from oil shale in a simple 1,5 source oi petroleum,

must be refined and of separate products before the shale be usedcommercially.

is to subject the petroleum oil to high `t oil are vaporized terfractionation 20 tures whereby portions and the vapors are recovered afThus, the usual of the where solvent is removed the petroleum reered asa rocess.

f recovering and inexpensive manner. Where oil shale is used as a theliquid lfractionated into a product obtained number oil canmethodemperaas gasoline, kerosene, gas oil and similar products. Thetemperatures to which the cr be either below the point terial issubjected may take place prior to the rials into commercial cuts.

the refining operation,

containing hydrocarbon 30 propane, butane, pentane, an

rials of other series which lmay into a liquid under pressure in theusual method being drocarbons from the n 35 are associated, by meantroleum oil. These compo removed from the oil men heat and are recoveredgases with 0 This material is a form .45 obtained, in.

" compound.

bilizng is a line lform of cut, the propane cut, or the cut, I use asshale oil 55 elated, r-or I may use` which they have which is a hydrocartained underA superatmospheric from the rock with` ude ma- 25 or abovethe point at which pyrolytic reactions separation of the mate- YAs aby-product of there is produced a gas compounds such as d analogousmatebe condensed a number of ways;

to rst absorb these hyxed gas wi th which they s of a high boilingpeunds are then usually struum by means of separately from the fixedbeen associated.

of natural gasoline and is usually further fractionated to remove smallell as of a fraction in minating compound. fraction is also is thepredominating product of this stastabilized natural gasobon liquid whenmainpressure, but

ospheric pressure. These stabilized thatv is, thebutane natural solventfor removing the which it the unstabilized is assonatural fB, by whichof the extractor 2. From the hopper, the crushed the sealed inletcompartment yApplication August 4, 1934, Serial No. '738,405

8 Claims. (Cl. 19E-14) a novel processpior of oilfrom oil shale boilinghydrocarbons,

recovery of the solvent from the shale may be eiiected. This separationof the solvent from `the spent shale is accomplished by converting thesolvent into the vapor state. By my present 1 invention, these vaporsare recovered along with lcondensable vapors produced in the petroleumrefinery, in the vapor recovery section of the refinery. v

The objects of my invention,

1. To provide novel apparatus for and methods of separating a solventfrom the extract in the process of extracting oil from shale.

2l. To provide novel means for recovering the solvent vapors removedfrom the spent shale 25 after extraction.

3. To utilize the lighter fractions of petroleum rening as an extractionmedium in the removal of shale oil and to circulate these fractinssubstantially continuously between the ex- 30 tractor and the petroleumrenery. Other ob` jects of my invention are apparent from thesespecifications.

My invention may best be described by reference to the accompanyingdrawing which is a 35 part of this specification. In this drawing Figurel is a diagrammatic layout of one embodiment of my invention.

Figure 2 is an elevation of a preferred form of extractor for use inconnection with my in- 4o vention.

Referring to Figure tank l, and is delivered to extractor the valve 3.

The oil shale is delivered to the4 Crusher 4, 45 where it is reduced toproper size, which I prefer'v shall be such that the crushed materialwill fall through a one inch screen and will on a half inch the oilshale passes to the screenl properly graded and delivered to theconveyor it is transferred to the feed hopper 1 thus, are: 20

1, solvent is contained in 2, through oil shale is delivered throughrotary valve 8 to 9 of the extractor,55

' discharged from rotary from which it passes through rotary valve I tothe extraction cylinder II.

The operations within the extraction cylinder can best be explained byreferring to Figure 2. The oil shaleV entering the cylinder from rotaryvalve I0 is passed into the rotating cylindrical compartment, I2a, bymeans ofthe deector vane rotating cylindrical compartment meets astrong'solution about to be discharged from the extraction cylinder il.The rotation of the compartment I 2a carries the shale forward andupward and discharges it into rotating compartment i221, where thesolution strength is somewhat weaker than that in compartment I2a. In asimilar manner the shale is carried reaches compartment 12d, intosolvent is delivered through the valve 3. The shale, leaving compartmentI2dv and delivered to the compartment I2e by defiector vane I3e, issubstantially free from shale oil, butA will be wet with solvent besidescarrying amounts of solvent by absorption and similar means. therotarycylinder I2e the spent shale is drained of its solvent and is passed bymeans of deflecto-r vane I3f to the compartment I 4. The spent shalewith its absorbed solvent is passed4 from the compartment I4 to theconveyor I5. The conveyor I5 is provided withY a heating jacket I6, intowhich suitable heating medium is admitted through the valve I1, anddischarged through While in the conveyor I5 the spent shale is heated tothe rotary valve I9, which discharges the spent shale into the sealedVoutlet compartment where it is subjected to a vacuum applied throughpipe 2l. This vacuum acts to eliminate the sol- The solvent enteringthrough the valve 3 into I the rotary compartment I2d, passes in contactwith the shale about to be discharged from the extraction cylinder. Itis then delivered consecutively to rotating cylinders I2C, I2b, and I 2ain counterow to the movement of the shale, and is then discharged fromthe extraction cylinder by outlet pipe 23.

Again referring to Figure 1, the spent shale is valve 22, to conveyor24, whichV delivers it to any convenient location.

The solution discharged from the extractor through `the gure, onlysufficient detail being shown to fully explain my invention.

The solution passing through valve enters the pump 29 which delivers itto the cracking still 30 where it is subjected to conditions favorableto cause pyrolytic reaction. After passing through the cracking still,the solution is delivered to the reaction chamber 3l and thedephlegmator 32, where a portion is condensed and is recirculatedthrough the cracking still 30 by the pump 34. The vapors from thedephlegmator 32 pass into the rectification portion of the cracking unitas represented by the rectangle 33. This rectangle here represents thevarious fractionating columns, condensers, storage tanks paratus makingup the balance of the cracking unit, including the separator in whichthe gases 'exhauster 55 including propane, butane etc. are separatedfrom the liquid components. These gases with their condensable vaporsare shown as leaving the cracking unit through the valve 35.

The solution passing through Valve 26 is delivered to the tube-still 36by the pump 31. In the tube-still 36 the solution is heated anddelivered to the fractionating column 38 from which as shown a number ofside cuts are removed. As shown, a gasoline cut is removed from the topof the column, passed through the condenser 39 and delivered to theseparator 40, the gasoline being withdrawn from the bottom of theseparator through valve 4I and the vapors and non-condensable gasesincluding propane and butane are Withdrawn from the separator throughvalve 42.

The vapors and ing unit through gases removed from the crackthe valveand/or removed 4from the topping unit through the valve 42, are

delivered totheA vapor recovery unit 43. This may be of any well knowntype and therefore only sufficient detail is shown to explain the operation in connection with this invention. The rectangle 44 representsthe usual-absorption unit with the necessary absorbers, compressors,stills, tanks, condensers, etc.V The liquid product comprising propane,butane and pentane is Withdrawn from the absorption unit through thepipe 45 to the stabilizer or column 46. The fixed gases', dissolved inthe liquid which is delivered through pipe 45, are removed through pipe41. The stabilized gasoline is removed from the bottom of the column anddelivered to the tank 48. Propane vapors may be removed through valve 49or butane vapors through valve 50, and delivered to the condenser 5I, inwhich they are liquefied and fromrwhich the liquid is delivered to tank52. The propane or butane may be delivered to the solvent storage tank Iby opening valve 53, or the natural gasoline may be delivered to tank Iby opening valve 54.

The exhauster 55 is connected on its suction side to the sealed inletcompartment 9 and removes therefrom solvent vapors Which enter thecompartment 9 through the rotary valve I0 and the air which enters thecompartment 9 through the rotary valve 8. I prefer that exhauster 55 beso adjusted that the pressure maintained withinY the sealed inletcompartment 9 be slightly above the pressure of the atmosphere. Thecompresses the gases and vapors recovery unit 43.

Exhauster 51 is connected on its suction side with the sealed'outletcompartment 20. I prefer exhauster 51 be so adjusted that it maintainsWithin the outlet compartment a pressure of less than half a' normalatmosphere. gases and vapors removed by exhauster 51 from the sealedoutlet compartment 20 are compressed comprises dissolving'shale-oil in ahydrocarbonn;

' oil shale while said hydrocarbon liquid that is gaseous at normaltemperatures and pressure by contacting the oil-shale with saidhydrocarbon delivered and applied to said is in the liquid phase,maintaining said hydrocarbon in the liquid phase while in contact withsaid oil-shale; withdrawing the solution; subjecting the solution,whilesaid solution still containssubstantial amounts of the solvent, to theaction of heat at such temperature that pyrolytic reactions take place;then separating the solution into fractions, including one fraction ofthe character of the solvent used; and returning a portion of saidfraction to the dissolving step.

2. The method of extracting oil-shale which comprises, dissolvingshale-oil in natural gasoline by contacting the cil-shale with naturalgasoline delivered and applied to said oil shale while maintained inliquid phase, maintaining said natural gasoline in the liquidphase whilein contact with said oil-shale; withdrawing the solution, thensubjecting the solution, while it still contains a substantial amount ofsaid solvent, to the action of heat at such temperature that pyrolyticreactions take place; then separating the solution into fractionsincluding one fraction analogous to said natural gasoline; and returninga portion of said latter" fraction to the dissolving step.

3. The method of extracting oil-shale which comprises dissolvingVshale-oil by contacting said oil-shale with butane delivered andapplied to said oil shale while maintained in the liquid phase,maintaining said butane in the liquid phase while in contact with saidoil-shale; withdrawing the solution; then subjecting the solution, whileit still contains a substantial amount of butane, to the action of heatat such temperature that pyrolytic reactions take place; then separatingthe solution into fractions, including one fraction of "butane; andreturning a portion of said butane fraction to the dissolving step.

4. The method of extracting oil-shale which comprises dissolvingshale-oil by contacting said oil-shale with propane delivered andapplied to said oil shale while maintained in the liquid phase,maintaining said propane in the liquid phase while in contact with saidoil-shale; withdrawing the solution; then subjecting the solution, whileit still contains a substantial amount of said propane, to the action ofheat at such temperature that pyrolytic reactions take place; thenseparating the solution into fractions including one fraction ofpropane; and returning a portion of said propane fraction to thedissolving step.

5. The mtehod of extracting petroleum bearing solid material whichcomprises dissolving a portion of the petroleum in a hydrocarbon liquidthat is gaseous at normal temperatures and pressure by contacting thepetroleum bearing solid material with said hydrocarbon delivered andapplied to said petroleum bearing solid material while said hydrocarbonis in the liquid phase, maintaining said hydrocarbon in the liquid phasewhile in contact with said petroleum bearing solid material; withdrawingthe solution; subjecting the solution, while said solution stillcontains substantial amounts of the solvent, to the action of heat atsuch temperature that pyrolytic reactions takey place; then separatingthe solution into fractions, including one fraction of the character ofthe solvent used; and returning a portion of said fraction to thedissolving step.

6. The method of extracting petroleum bearing solid material whichcomprises, dissolvinga portion of the petroleum in natural gasoline bycontacting the petroleum bearing solid material with "natural gasolinedelivered and applied to said petroleum bearing solid material whilemaintained in the liquid phase, maintaining said-natural gasoline in theliquid phase, while in contact with said petroleum bearing solidmaterial; withdrawing the solution, then subjecting the solution, whileit still contains a substantial amount of said solvent, to the action ofheat at such temperature that pyrolytic reactions take place; thenseparating the solution into' fractions including one fraction analogousto said natural gasoline; tion of said latter fraction to the dissolvingstep.

'7. The method of extracting petroleum bearing solid material whichcomprises dissolving a portion of the petroleum by contacting saidpetroleum bearing solid material with butane delivered and applied tosaid petroleum bearing solid material while maintained in the liquidphase, maintaining said butane in the liquid phase while in contact withsaid petroleum bearing 'solid material; withdrawing the solution; thensubjecting the solution, while it still contains a substantial amount ofbutane, to the action of heat at s-uch temperature that pyrolyticreactions take place; then separating the solution into fractions,including one fraction of butane; and returning a portion of said butanefraction to the dissolving step.

8. The method of extracting petroleum bearing solid material whichcomprises dissolving a portion of the petroleum by contacting saidpetroleum bearing solid material with propane delivered and applied tosaid petroleum bearing solid material While maintained in the liquidphase, maintaining said propane in the liquid phase while in contactwith said petroleum bearing solid material; withdrawing the solution;then subjecting the solution, While it still contains a substantialamount of said propane, to the action of heat at such temperature thatpyrolytic reactions take place; then separating the solution intofractions including one fraction of propane; and returning a portion ofsaid propane fraction to the dissolving step.

HENRY ROSENTHAL.

and returning a por-y

